WO2023211390A1 - Procédé de récupération de polyoléfines à partir de déchets, et produit polyoléfinique ainsi récupéré - Google Patents
Procédé de récupération de polyoléfines à partir de déchets, et produit polyoléfinique ainsi récupéré Download PDFInfo
- Publication number
- WO2023211390A1 WO2023211390A1 PCT/TR2022/050375 TR2022050375W WO2023211390A1 WO 2023211390 A1 WO2023211390 A1 WO 2023211390A1 TR 2022050375 W TR2022050375 W TR 2022050375W WO 2023211390 A1 WO2023211390 A1 WO 2023211390A1
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- WO
- WIPO (PCT)
- Prior art keywords
- nonsolvent
- polyolefin
- vegetable oil
- mixture
- polypropylene
- Prior art date
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000011084 recovery Methods 0.000 title claims description 15
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000008158 vegetable oil Substances 0.000 claims abstract description 51
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- -1 polypropylene Polymers 0.000 claims description 102
- 239000004743 Polypropylene Substances 0.000 claims description 75
- 229920001155 polypropylene Polymers 0.000 claims description 75
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 60
- 239000004698 Polyethylene Substances 0.000 claims description 27
- 229920000573 polyethylene Polymers 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 23
- 239000000828 canola oil Substances 0.000 claims description 22
- 235000019519 canola oil Nutrition 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 34
- 229920000642 polymer Polymers 0.000 abstract description 33
- 238000004064 recycling Methods 0.000 abstract description 18
- 238000000605 extraction Methods 0.000 abstract description 12
- 230000003247 decreasing effect Effects 0.000 abstract description 8
- 239000010812 mixed waste Substances 0.000 abstract description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000013502 plastic waste Substances 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 2
- 235000006008 Brassica napus var napus Nutrition 0.000 description 2
- 240000000385 Brassica napus var. napus Species 0.000 description 2
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008169 grapeseed oil Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0217—Mechanical separating techniques; devices therefor
- B29B2017/0224—Screens, sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0286—Cleaning means used for separation
- B29B2017/0289—Washing the materials in liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Definitions
- the present invention relates to a method for recycling polyolefins from waste products including polypropylene, polyethylene, copolymers and mixtures thereof.
- the present invention generally relates to using vegetable oils and their mixtures for dissolving, dissolving via melting, selectively dissolving polyolefins, and their extraction and recovery from the multicomponent plastic waste or plastic waste mixtures.
- This solvent-based extraction method generally comprises the dissolution of the collected material in a solvent, filtration for the removal of impurities, precipitation of the polymer, separation of the recovered polymer, thorough washing, and drying.
- a prior art JP2002003860A discloses an apparatus and a method for converting waste plastics into oil/fuel by melting the waste plastics in vegetable oil.
- the plastic from mixed household waste is dissolved in solvent oil like edible oil, vegetable oil and mineral oil for dehydration, dechlorination, and enhancing the calorific value of plastic.
- W09909092A1 discloses a method for reprocessing polymeric products, for example tyres and PVC coated metal products, wherein the process includes the step of treating the polymeric product with at least one vegetable oil, and subjecting the vegetable oil in contact with the polymeric product to an elevated temperature for a sufficient time to liquify the polymer. The liquified polymer is then separated from the metals and canvas/belting products in the polymeric product in order to recover the polymer, metals, and canvas/belting products.
- the primary object of the present invention is to overcome the abovementioned shortcomings of the prior art.
- a further object of the invention is to develop an effective recycling method that can extract polyolefins in their pure form from mixed wastes and enables the use of vegetable oils as solvents.
- Another object of the present invention is to provide a method with optimum temperature for the processability and separability of each polyolefin type.
- Another object of the present invention is to provide a method for recycling coated polyolefin packaging films (metallic, poly (vinyl alcohol), poly (vinylidene chloride), etc. coated) using vegetable oil as the solvent and alkanes as the nonsolvent.
- Another object of the present invention is to replace the solvents currently used, petroleumbased decalin, tetrachloroethylene, xylene, toluene/petroleum ether or any other solvents with environmentally benign vegetable oils.
- the present invention provides a method for selectively extracting and recovering pure polyolefin polymers from wastes containing a plurality of polymers, by using one or more solvents at different temperatures for selectively dissolving one or more polymers from the mixture.
- the present invention generally presents a vegetable oil-based recycling method basically comprising the three main steps as extraction of waste polyolefins from mixed waste by dissolving in vegetable oil, advanced purification of polyolefins using sequential filters by progressively decreasing pore sizes in each filter, and precipitation of the selected and/or purified polyolefins in a liquid that is miscible with the vegetable oil.
- a method for the extraction and recovery of polyolefins from waste mixture essentially comprising the step of (i) mixing the waste material into a vegetable oil, selectively extracting polyolefins from mixed waste by heating at a certain temperature depending on the polyolefin type, (ii) separation of undissolved materials from the solution by filtration through a coarse filter, (iii) purification of the filtered mixture including the dissolved polyolefin by a fine filter while maintaining its initial temperature, (iv) precipitation of the purified mixture in a liquid which is miscible with said vegetable oil and does not dissolve the said polyolefin at said precipitation conditions, (v) separation of precipitated polyolefin from the vegetable oil/nonsolvent mixture, (vi) thoroughly washing the precipitated polyolefin to purify and remove remaining oils, (vii) drying the separated polyolefin, (viii) separation of the vegetable oil/nonsolvent mixture via distillation, with the recovered nonsolvent retrieved from the top of a distillation column and
- Another aspect of the said recycling method provides high purity polyolefins from mixed materials using vegetable oils as solvent.
- This method includes the following steps: selectively dissolving polyolefins in plastic waste mixtures using vegetable oils as the solvent, performing advanced purification of polyolefins using sequential filters by progressively decreasing pore sizes in each filter, separation of vegetable oil from filtered and purified polyolefins via precipitation of filtered and purified solution in the presence of a nonsolvent that dissolves vegetable oil, separation and thoroughly washing of precipitates, drying of recycled polymers.
- the vegetable oil/nonsolvent ratio used in precipitation step is greater than 1: 1 (v/v) and preferably greater than 1:3 (v/v).
- the waste mixture concentration in the vegetable oil is ranging from 5 to 30 % by weight.
- the waste mixture comprises polyethylene and polypropylene together, and the waste mixture is mixed into a vegetable oil by heating at a temperature ranging from 140 to 155 °C to selectively dissolve and recover polyethylene from the mixture first according to the abovementioned steps, and then re-mixing the unfiltered portion into a vegetable oil again and heating up to 185 °C to dissolve and recover polypropylene according to the abovementioned steps.
- polyolefin product(s) with a purity of greater than 99% is recovered in accordance with said method.
- polyolefin product(s) with a residual solvent of lower than 1% is recovered in accordance with said method.
- polyolefin product(s) with a nonsolvent content of lower than 1% recovered in accordance with said method in accordance with said method.
- Fig. 1 and 2 show FTIR spectra of canola oil, waste carpet material, coarse filter waste, pure polypropylene and recycled polypropylene polymer according to example 1.
- Fig. 3 and 4 show FTIR spectra of recycled polyethylene in comparison to pure polyethylene and recycled polypropylene in comparison to pure polypropylene according to example 2.
- Fig. 5, 6 and 7 show FTIR spectra of recycled polypropylene precipitated in heptane at 7, 24, and 98 °C according to example 3.
- Fig. 8 shows a FTIR spectra of recycled polypropylene, precipitated in heptane at 98 °C varying the solvent to nonsolvent ratios according to example 4.
- a method for the recovery of polyolefins from a waste material comprising the step of mixing the waste material into a vegetable oil and heating at a temperature ranging from 120 °C to 200 °C for obtaining a mixture containing dissolved polyolefin, filtering the mixture by a coarse filter, purification of the filtered mixture including dissolved polyolefin by further filtration through a second filter, precipitation of the purified polyolefin by adding filtered mixture at its initial temperature into a liquid which is a nonsolvent that is miscible with said vegetable oil, at or below the boiling point of the nonsolvent, separation of precipitated solid polyolefin from the vegetable oil/nonsolvent mixture, washing the separated polyolefin with the nonsolvent, and drying under the inert atmosphere.
- the method further comprises a step of fractionation of the vegetable oil/nonsolvent mixture via distillation, with the recovered nonsolvent retrieved from a distillation column and the recovered vegetable oil retrieved from the bottom of said distillation setup.
- the first coarse filter has a pore size ranging from 5 to 40 pm.
- the second filter has a pore size ranging from 100 nm to 450 nm.
- the method further comprises a step of passing the filtered mixture through an adsorption column such as activated carbon column.
- an adsorption column such as activated carbon column.
- the impurities in the resulting mixture are removed.
- An average pore size of 5 micron and above is sufficient for coarse filtration, preferably 37 micron (400 mesh).
- a second filtration is required using a filter with an average pore size of 1 micron and below, preferably 0.1 micron.
- the method further comprises a step of washing the resultant polyolefin in boiling nonsolvent under reflux when it is precipitated in heptane at a temperature ranging from 20 °C to 30 °C between the step (iv) and the step (vi).
- the method further comprises a step of washing the resultant polyolefin in boiling heptane under reflux when it is precipitated in heptane at a temperature ranging from 22 °C to 37 °C between the step (iv) and the step (vi).
- the input waste material may be any organic and inorganic mixture containing polyolefins, preferably at least 30% polyolefin.
- said polyolefin is a polypropylene or polyethylene, copolymer or combination thereof.
- said vegetable oil is a form of triglycerides which is an ester formed by the addition of three fatty acids to glycerol.
- Soybean oil, grape seed oil, and cocoa butter are examples of fats from seeds.
- Olive oil, palm oil, and rice bran oil are examples of fats from other parts of fruits.
- said vegetable oil can be selected from the list comprising canola oil, sunflower oil, cottonseed oil, corn, olive, peanut, and coconut oil or a combination of two or more thereof.
- dissolution and polyolefin extraction temperatures are 140 °C and above, preferably 155 °C, for wastes containing only polyethylene type polyolefin, and 170 °C and above, preferably 185 °C, for wastes containing only polypropylene type polyolefin.
- extraction of the polyethylene first at 155 °C, followed by the extraction of the remaining polypropylene at 185 °C.
- the nonsolvent is an alkane and preferably an aliphatic or cyclic saturated hydrocarbon, with a number of carbon atoms equal to 6 to 9.
- said nonsolvent an aliphatic or cyclic saturated hydrocarbon, with a number of carbon atoms higher than 6.
- the aliphatic or cyclic saturated hydrocarbon comprises seven carbon atoms with one chiral carbon atom.
- the nonsolvent is heptane, hexane, or cyclohexane.
- the vegetable oil/nonsolvent ratio used in precipitation step is greater than 1: 1 (v/v) and preferably greater than 1:3 (v/v).
- the waste mixture including the polyolefin was in a concentration ranging from 5 to 30 % by weight in the recycling solvent.
- the precipitation of the polyolefin to be recovered is carried out by dripping hot solution into nonsolvent at or slightly below its boiling point temperature.
- nonsolvent for example, if heptane is used as a nonsolvent, the precipitation temperature will be 98 °C or below.
- some solvent may remain in and on the surface of polyolefin particles and they may be washed and rinsed well with the nonsolvent to remove.
- the drying process is carried out under inert atmosphere, optionally under heat and/or vacuum to reduce the risk of oxidation by removing the oxygen from the environment and to ensure better removal of the nonsolvent.
- Example 1 Extraction and recovery of high purity polypropylene from waste carpet.
- a waste carpet comprising cotton, wool, jute, PAN, PET, PU and SBR was shredded into small pieces. Recycling process of the polypropylene in said waste carpet includes a dissolution step, hot coarse filtration followed by hot fine filtration, precipitation step, separation of precipitated polypropylene, thorough washing, and drying.
- dissolution step required amount of pre-processed feedstock material was placed into the canola oil. The mixture was stirred by a magnetic stirrer at 185 °C for 2 hours under reflux.
- filtration step two stage filtration was applied for the removal of impurities (coarse undissolved materials and pigments, respectively).
- a stainless steel mesh with a mesh pore size of 37 pm was used as a coarse filter to remove coarse undissolved materials.
- a filtration cell with an active filtration area of 14.6 cm 2 was used for the hot fine filtration.
- the filtration cell was wrapped by a flexible heating tape and heated to 190 °C before filtration.
- a PTFE membrane with a pore size of 0.2 pm was used for the removal of the pigments in the filtration cell.
- the solution was filtered directly into the heptane for precipitation.
- the pigments were captured by the PTFE membrane during the hot filtration and polypropylene polymer free from pigments precipitated in the heptane.
- canola oil to nonsolvent ratio was selected as 1:3 v/v.
- the waste carpet/canola solution was filtered through the membrane into the heptane at 98°C.
- the amount of heptane used in the precipitation process is 577.49 ml, the amount of recovered heptane is 421.13 ml, and the recovery efficiency is 78.12%.
- the amount of polypropylene in the waste is 80.75%, the amount of recovered polypropylene is 76.37%, and the recovery efficiency is 95%.
- a spectrometer was used for FTIR analysis of canola oil, waste carpet material, coarse filter waste, pure polypropylene and recycled polypropylene polymer in order to confirm that the recycled polypropylene obtained via the solvent-based recycling using canola oil as the solvent showed similar structure and composition to the pure polypropylene freshly synthesized from petroleum-based products.
- a minimum of 32 scans with a signal resolution of 4 cm 1 within the 4000-650 cm 1 range were averaged to obtain the spectra.
- the FTIR spectra obtained are presented in Fig. 1 and Fig. 2.
- FTIR spectrum of recycled polypropylene polymer confirmed that recycled polypropylene was free from the solvent (canola oil) as signals of the canola oil, mainly the peak at 1742 cm 1 corresponding to carbonyl peak, were not observed in the spectrum of the recycled polypropylene polymer.
- Example 2 Selective dissolution and recovery of polymers from polypropylene and polyethylene mixture using canola oil as the solvent and heptane as the nonsolvent.
- the present invention provides a method for recovering both polyethylene and polypropylene from a mixture of plastics. Since the waste contains both polyethylene and polypropylene, the polyethylene is first dissolved in vegetable oil at 155 °C, and the insoluble polypropylene is filtered off.
- the aforementioned processes are used to recover dissolved polypropylene wherein said process comprises advanced purification of polyethylene using using sequential filters by progressively decreasing pore sizes in each filter, separation of vegetable oil from filtered and purified polyethylene via precipitation of filtered and purified solution into heptane that dissolves vegetable oil, separation and thoroughly washing of precipitates, and drying of recycled polyethylene.
- the residual waste that does not contain polyethylene is dissolved in canola oil by heating at 185 °C for the recovery of polypropylene.
- the procedures of filtering, precipitation, separation, washing, and drying are performed throughout the polypropylene recovery process.
- Polyethylene and polypropylene are rather simple in their chemical nature, consisting of only carbon and hydrogen atoms linked by covalent bonds, resulting in a small number of signals in FTIR spectrum as seen in Fig. 3 and Fig. 4.
- FTIR spectrum of pure polyethylene characteristic peaks located at 2919 cm 1 , 2850 cm 1 , 1470 cm 1 , and 718 cm 1 are observed. While the peaks at 2919 and 2850 cm 1 are assigned to -CH 2 asymmetric and symmetric stretchings, respectively; the peak at 1464 corresponds to the bending vibration of -CH 2 and 730 cm 1 to -CH 2 rocking.
- Peaks at 1167 cm 1 , 998 cm 1 , 842 cm 1 were assigned to characteristic vibrations for isotactic polypropylene.
- the peaks observed in the spectrum of the recycled polypropylene were identical to the characteristic peaks of pure polypropylene which showed that the recycled polypropylene obtained by the recycling process applied were the same as the pure polypropylene and in pure state (free from polyethylene and vegetable oil used).
- Example 3 Precipitation of extracted polypropylene at different nonsolvent temperatures.
- Example 4 Precipitation of dissolved polypropylene in various solvent - nonsolvent ratios.
- Example 5 Washing the final polypropylene in boiling heptane under reflux.
- the claimed invention comprising a method and/or a solvent-nonsolvent combination brings the advantages of:
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Abstract
La présente invention porte sur un procédé d'extraction sélective et de récupération de polymères polyoléfiniques purs à partir de déchets contenant une pluralité de polymères, en utilisant un ou plusieurs solvants à différentes températures pour dissoudre sélectivement un ou plusieurs polymères du mélange. L'invention présente de façon générale un procédé de recyclage à base d'huile végétale comprenant essentiellement les trois étapes principales suivantes : extraction de déchets de polyoléfines à partir de déchets mixtes par dissolution dans de l'huile végétale, purification avancée de polyoléfines à l'aide de filtres séquentiels ayant des tailles de pores diminuant progressivement dans chaque filtre, et précipitation des polyoléfines sélectionnées et/ou purifiées dans un liquide qui est miscible à l'huile végétale. L'invention concerne en outre un produit polyoléfinique ayant une pureté supérieure à 99 % récupéré par le procédé.
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PCT/TR2022/050375 WO2023211390A1 (fr) | 2022-04-26 | 2022-04-26 | Procédé de récupération de polyoléfines à partir de déchets, et produit polyoléfinique ainsi récupéré |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5119073A (en) * | 1974-08-08 | 1976-02-16 | Mitsubishi Heavy Ind Ltd | Haikibutsuyori purasuchitsukuo kaishusuruhoho |
WO1999009092A1 (fr) | 1997-08-21 | 1999-02-25 | Edsview Belleggings (Proprietary) Limited | Retraitement de produits polymeres |
JP2002003860A (ja) | 2000-06-19 | 2002-01-09 | Namura Shipbuilding Co Ltd | 廃プラスチック類の溶融油化装置 |
EP3112406A1 (fr) * | 2015-06-30 | 2017-01-04 | The Procter and Gamble Company | Procédé de purification de polyoléfines contaminées |
US20170298207A1 (en) * | 2014-10-03 | 2017-10-19 | Polystyvert Inc. | Processes for recycling polystyrene waste |
US20190390031A1 (en) * | 2018-06-20 | 2019-12-26 | The Procter & Gamble Company | Method For Purifying Reclaimed Polypropylene |
US20210380777A1 (en) * | 2018-10-26 | 2021-12-09 | Polystyvert Inc. | Processes for recycling polystyrene waste and/or polystyrene copolymer waste |
-
2022
- 2022-04-26 WO PCT/TR2022/050375 patent/WO2023211390A1/fr active Search and Examination
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5119073A (en) * | 1974-08-08 | 1976-02-16 | Mitsubishi Heavy Ind Ltd | Haikibutsuyori purasuchitsukuo kaishusuruhoho |
WO1999009092A1 (fr) | 1997-08-21 | 1999-02-25 | Edsview Belleggings (Proprietary) Limited | Retraitement de produits polymeres |
JP2002003860A (ja) | 2000-06-19 | 2002-01-09 | Namura Shipbuilding Co Ltd | 廃プラスチック類の溶融油化装置 |
US20170298207A1 (en) * | 2014-10-03 | 2017-10-19 | Polystyvert Inc. | Processes for recycling polystyrene waste |
EP3112406A1 (fr) * | 2015-06-30 | 2017-01-04 | The Procter and Gamble Company | Procédé de purification de polyoléfines contaminées |
US20190390031A1 (en) * | 2018-06-20 | 2019-12-26 | The Procter & Gamble Company | Method For Purifying Reclaimed Polypropylene |
US20210380777A1 (en) * | 2018-10-26 | 2021-12-09 | Polystyvert Inc. | Processes for recycling polystyrene waste and/or polystyrene copolymer waste |
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